Ceramic article with reduced surface defect density

ABSTRACT

A machined ceramic article having an initial surface defect density and an initial surface roughness is provided. The machined ceramic article is heated to a temperature range between about 1000° C. and about 1800° C. at a ramping rate of about 0.1° C. per minute to about 20° C. per minute. The machined ceramic article is heat-treated in air atmosphere. The machined ceramic article is heat treated at one or more temperatures within the temperature range for a duration of up to about 24 hours. The machined ceramic article is then cooled at the ramping rate, wherein after the heat treatment the machined ceramic article has a reduced surface defect density and a reduced surface roughness.

RELATED APPLICATIONS

This present application is a continuation of U.S. patent applicationSer. No. 13/659,813, filed Oct. 24, 2012, which claims the benefit under35 U.S.C. § 119(e) of U.S. Provisional Application No. 61/601,458, filedFeb. 21, 2012, the entire contents of which are hereby incorporated byreference herein.

TECHNICAL FIELD

Embodiments of the present invention relate, in general, to a heattreatment process that minimizes surface defect density and ceramicarticles processed using a heat treatment process.

BACKGROUND

In the semiconductor industry, devices are fabricated by a number ofmanufacturing processes producing structures of an ever-decreasing size.Some manufacturing processes such as plasma etch and plasma cleanprocesses expose a substrate to a high-speed stream of plasma to etch orclean the substrate. The plasma may be highly corrosive, and may corrodeprocessing chambers and other surfaces that are exposed to the plasma.This corrosion may generate particles, which frequently contaminate thesubstrate that is being processed, contributing to device defects.

As device geometries shrink, susceptibility to defects increases, andparticle contaminant requirements become more stringent. Accordingly, asdevice geometries shrink, allowable levels of particle contamination maybe reduced. To minimize particle contamination introduced by plasma etchand/or plasma clean processes, chamber materials have been developedthat are resistant to plasmas. Examples of such plasma resistantmaterials include ceramics composed to Al₂O₃, AlN, SiC and Y₂O₃.However, the plasma resistance properties of these ceramic materials maybe insufficient for some applications. For example, plasma resistantceramic lids and/or nozzles that are manufactured using traditionalceramic manufacturing processes may produce unacceptable levels ofparticle contamination when used in plasma etch processes ofsemiconductor devices with critical dimensions of 45 nm or 32 nm.

SUMMARY

In one embodiment, a ceramic article having an initial surface defectdensity and an initial surface roughness is provided. The ceramicarticle is heated to a temperature range between about 1000° C. andabout 1800° C. at a ramping rate of about 0.1° C. per minute to about20° C. per minute. The ceramic article is heat treated at one or moretemperatures within the temperature range for a duration of up to about24 hours. The ceramic article is then cooled at the ramping rate. Afterthe heat treatment, the ceramic article has a reduced surface defectdensity and a reduced surface roughness, and may additionally have agreater resistance to plasma.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is illustrated by way of example, and not by wayof limitation, in the figures of the accompanying drawings in which likereferences indicate similar elements. It should be noted that differentreferences to “an” or “one” embodiment in this disclosure are notnecessarily to the same embodiment, and such references mean at leastone.

FIG. 1A illustrates an exemplary architecture of a manufacturing system,in accordance with one embodiment of the present invention;

FIG. 1B illustrates a process for heat treating a ceramic article, inaccordance with one embodiment of the present invention;

FIG. 2A shows micrographs of a ceramic article at a 10,000-foldmagnification before the ceramic article is processed using a heattreatment, and after the ceramic article has been processed using heattreatments of various temperatures, in accordance with embodiments ofthe present invention;

FIG. 2B shows micrographs of an HPM composite ceramic article at a4,000-fold magnification before the ceramic article is processed using aheat treatment, and after the ceramic article has been processed usingheat treatments of various temperatures, in accordance with embodimentsof the present invention;

FIG. 3A illustrates surface profiles of the ceramic articles of FIGS.2A-2B before and after the heat treatment, in accordance with oneembodiment of the present invention;

FIG. 3B illustrates a phase composition comparison of an HPM ceramiccomposite before heat treatment, after a 1200° C. heat treatment andafter a 1680° C. heat treatment;

FIG. 4A shows micrographs of a solid yttria ceramic article at a10,000-fold magnification before and after the solid yttria ceramicarticle is processed using a heat treatment, in accordance with oneembodiment of the present invention;

FIG. 4B shows micrographs of a solid yttrium oxide ceramic article at a4,000-fold magnification before and after the solid yttrium oxideceramic article is processed using the heat treatment, in accordancewith one embodiment of the present invention;

FIG. 5 illustrates surface profiles of the solid yttrium oxide ceramicarticle of FIGS. 4A-4B before and after the heat treatment, inaccordance with one embodiment of the present invention;

FIG. 6 illustrates surface particle count of an HPM composite ceramicbefore and after heat treatment, in accordance with one embodiment ofthe present invention; and

FIG. 7 illustrates surface particle count (in thousands of particles) ofan HPM composite ceramic before heat treatment and during heat treatmentat various temperatures, in accordance with embodiments of the presentinvention.

DETAILED DESCRIPTION OF EMBODIMENTS

Embodiments of the invention are directed to a process for heat treatinga ceramic article, and to a ceramic article processed using the heattreatment. In one embodiment, a ceramic article having an initialsurface defect density and an initial surface roughness is provided. Theceramic article may be a hot pressed or sintered ceramic article thathas been machined (e.g., that has been polished, ground, had holesdrilled in it, etc.). The ceramic article may also be a hot pressed orsintered ceramic article that has not been machined. The ceramic articlemay be, for example, a ceramic lid or nozzle for a plasma etcher (alsoknown as a plasma etch reactor). The ceramic article is heated to atemperature range between about 1000° C. and about 1800° C. at a rampingrate of about 0.1° C. per minute to about 20° C. per minute. The ceramicarticle is heat treated at one or more temperatures within thetemperature range for a duration of up to about 24 hours. The ceramicarticle is then cooled at the ramping rate. After the heat treatment,the ceramic article has a reduced surface defect density and a reducedsurface roughness, and may additionally have a greater resistance toplasma. Moreover, dimensions of the ceramic article may experiencelittle to no change as a result of the heat treatment.

In one embodiment, a furnace performs a heat treatment process on aceramic article having an initial surface defect and an initial surfaceroughness. The furnace heats the ceramic article at a ramping rate ofabout 0.1° C. per minute to about 20° C. per minute until the ceramicarticle reaches a specified temperature or temperature range. Thespecified temperature range may vary from about 1000° C. to about 1800°C., and the specified temperature may be a temperature within thespecified temperature range. The furnace heat treats the ceramic articleat the specified temperature and/or other specified temperatures withinthe temperature range for a duration of up to about 24 hours. Thefurnace then cools the ceramic article at the ramping rate. After theheat treatment, the ceramic article has a reduced surface defect densityand a reduced surface roughness, and may additionally have a greaterresistance to plasma.

Embodiments of the invention reduce the surface roughness and surfacedefect density of processed ceramic articles, and minimize surfaceparticles on the ceramic articles. Such heat treated ceramic articleshave a reduced number of high energy bonds (broken bonds), and mayproduce a significantly lower amount of particle contamination when usedin semiconductor processes that apply plasmas (e.g., plasma etch andplasma clean processes). For example, ceramic lids and nozzles foretcher machines may be heat treated to minimize particle contaminationintroduced during plasma etch processes. Thus, semiconductorsmanufactured using the heat treated ceramic articles described hereinmay have a lower defect count and may result in reduced scrap rates.

The term “heat treating” is used herein to mean applying an elevatedtemperature to a ceramic article, such as by a furnace. The term“machined ceramic article” refers to a ceramic article that has beensurface ground, polished, drilled, abraded, cut, or otherwise processedwith machine tools. When the terms “about” and “approximate” are usedherein, this is intended to mean that the nominal value presented isprecise within ±10%.

Some embodiments are described herein with reference to using a furnaceto perform a heat treatment. However, it should be understood that otherheat treatment techniques may also be used to perform the described heattreatment. Some examples of additional heat treatment techniques thatmay be used include a laser surface treatment (also referred to as laserheat treatment), an electron beam (e-beam) surface treatment (alsoreferred to as e-beam heat treatment), a flame surface treatment (alsoreferred to as a flame heat treatment), and a high temperature plasmatreatment.

Note also that some embodiments are described herein with reference toceramic lids and ceramic nozzles used in plasma etchers forsemiconductor manufacturing. However, it should be understood that suchplasma etchers may also be used to manufacture micro-electro-mechanicalsystems (MEMS)) devices. Additionally, the heat treated ceramic articlesdescribed herein may be other structures that are exposed to plasma. Forexample, the ceramic articles may be rings, walls, bases, gasdistribution plates, shower heads, substrate holding frames, etc. of aplasma etcher, a plasma cleaner, a plasma propulsion system, and soforth. Moreover, embodiments are described herein with reference toceramic articles that cause reduced particle contamination when used ina process chamber for plasma rich processes. However, it should beunderstood that the ceramic articles discussed herein may also providereduced particle contamination when used in process chambers for otherprocesses such as plasma enhanced chemical vapor deposition (PECVD),plasma enhanced physical vapor deposition (PEPVD), plasma enhancedatomic layer deposition (PEALD), and so forth, and non-plasma etchers,non-plasma cleaners, chemical vapor deposition (CVD) furnaces, physicalvapor deposition (PVD) furnaces, and so forth.

FIG. 1A illustrates an exemplary architecture of a manufacturing system,in accordance with one embodiment of the present invention. Themanufacturing system 100 may be a ceramics manufacturing system. In oneembodiment, the manufacturing system 100 includes a furnace 105 (e.g., aceramic furnace such as a kiln), an equipment automation layer 115 and acomputing device 120. In alternative embodiments, the manufacturingsystem 100 may include more or fewer components. For example, themanufacturing system 100 may include only the furnace 105, which may bea manual off-line machine.

Furnace 105 is a machine designed to heat articles such as ceramicarticles. Furnace 105 includes a thermally insulated chamber, or oven,capable of applying a controlled temperature on articles (e.g., ceramicarticles) inserted therein. In one embodiment, the chamber ishermitically sealed. Furnace 105 may include a pump to pump air out ofthe chamber, and thus to create a vacuum within the chamber. Furnace 105may additionally or alternatively include a gas inlet to pump gasses(e.g., inert gasses such as Ar or N₂) into the chamber.

Furnace 105 may be a manual furnace having a temperature controller thatis manually set by a technician during processing of ceramic articles.Furnace 105 may also be an off-line machine that can be programmed witha process recipe. The process recipe may control ramp up rates, rampdown rates, process times, temperatures, pressure, gas flows, and so on.Alternatively, furnace 105 may be an on-line automated furnace that canreceive process recipes from computing devices 120 such as personalcomputers, server machines, etc. via an equipment automation layer 115.The equipment automation layer 115 may interconnect the furnace 105 withcomputing devices 120, with other manufacturing machines, with metrologytools and/or other devices.

The equipment automation layer 115 may include a network (e.g., alocation area network (LAN)), routers, gateways, servers, data stores,and so on. Furnace 105 may connect to the equipment automation layer 115via a SEMI Equipment Communications Standard/Generic Equipment Model(SECS/GEM) interface, via an Ethernet interface, and/or via otherinterfaces. In one embodiment, the equipment automation layer 115enables process data (e.g., data collected by furnace 105 during aprocess run) to be stored in a data store (not shown). In an alternativeembodiment, the computing device 120 connects directly to the furnace105.

In one embodiment, furnace 105 includes a programmable controller thatcan load, store and execute process recipes. The programmable controllermay control temperature settings, gas and/or vacuum settings, timesettings, etc. of heat treat processes. The programmable controller maycontrol a chamber heat up, may enable temperature to be ramped down aswell as ramped up, may enable multi-step heat treating to be input as asingle process, and so forth. The programmable controller may include amain memory (e.g., read-only memory (ROM), flash memory, dynamic randomaccess memory (DRAM), static random access memory (SRAM), etc.), and/ora secondary memory (e.g., a data storage device such as a disk drive).The main memory and/or secondary memory may store instructions forperforming heat treatment processes described herein.

The programmable controller may also include a processing device coupledto the main memory and/or secondary memory (e.g., via a bus) to executethe instructions. The processing device may be a general-purposeprocessing device such as a microprocessor, central processing unit, orthe like. The processing device may also be a special-purpose processingdevice such as an application specific integrated circuit (ASIC), afield programmable gate array (FPGA), a digital signal processor (DSP),network processor, or the like. In one embodiment, programmablecontroller is a programmable logic controller (PLC).

In one embodiment, furnace 105 is programmed to execute a recipe thatwill cause the furnace 105 to heat treat a machined ceramic articleusing a heat treatment process described with reference to FIG. 1B.

FIG. 1B is a flow chart showing a process 150 for heat treating aceramic article, in accordance with one embodiment of the presentinvention. At block 155 of process 150, a machined ceramic article isprovided (e.g., to a furnace or kiln). In one embodiment, the ceramicarticle is automatically loaded into a furnace by a loader. The ceramicarticle may be formed from a bulk ceramic such as Y₂O₃ (yttria oryttrium oxide), Y₄Al₂O₉ (YAM), Al₂O₃ (alumina) Y₃Al₅O₁₂ (YAG), YAlO3(YAP), Quartz, SiC (silicon carbide) Si₃N₄ (silicon nitride) Sialon, AlN(aluminum nitride), AlON (aluminum oxynitride), TiO₂ (titania), ZrO₂(zirconia), TiC (titanium carbide), ZrC (zirconium carbide), TiN(titanium nitride), TiCN (titanium carbon nitride) Y₂O₃ stabilized ZrO₂(YSZ), and so on. The ceramic article may also be a ceramic compositesuch as Y₃Al₅O₁₂ distributed in Al₂O₃ matrix, Y₂O₃—ZrO₂ solid solutionor a SiC—Si₃N₄ solid solution. The ceramic article may also be a ceramiccomposite that includes a yttrium oxide (also known as yttria and Y₂O₃)containing solid solution. For example, the ceramic article may be ahigh performance material (HPM) that is composed of a compound Y₄Al₂O₉(YAM) and a solid solution Y₂-xZr_(x)O₃ (Y₂O₃—ZrO₂ solid solution). Notethat pure yttrium oxide as well as yttrium oxide containing solidsolutions may be doped with one or more of ZrO₂, Al₂O₃, SiO₂, B₂O₃,Er₂O₃, Nd₂O₃, Nb₂O₅, CeO₂, Sm₂O₃, Yb₂O₃, or other oxides.

The ceramic article may be a sintered ceramic article that was producedfrom a ceramic powder or a mixture of ceramic powders. For example, theHPM ceramic composite may be produced from a mixture of a Y₂O₃ powder, aZrO₂ powder and an Al₂O₃ powder. In one embodiment, the HPM ceramiccomposite contains 77% Y₂O₃, 15% ZrO₂ and 8% Al₂O₃. In anotherembodiment, the HPM ceramic composite contains 63% Y₂O₃, 23% ZrO₂ and14% Al₂O₃. In still another embodiment, the HPM ceramic compositecontains 55% Y₂O₃, 20% ZrO₂ and 25% Al₂O₃. Relative percentages may bein molar ratios. For example, the HPM ceramic composite may contain 77mol % Y₂O₃, 15 mol % ZrO₂ and 8 mol % Al₂O₃. Other distributions ofthese ceramic powders may also be used for the HPM material.

If a mixture of ceramic powders was used to create the ceramic article,these powders may have been combined into a granular powder by spraydrying. The granular powder may have subsequently been compacted byunidirectional mechanical pressing or cold isostatic pressing prior toperforming a hot pressing or sintering process. The sintering processtypically changes the size of the ceramic article by an uncontrolledamount. Due at least in part to this change in size, the ceramic articleis typically machined after the sintering process is completed. Themachining may include surface grinding and/or polishing the ceramicarticle, drilling holes in the ceramic article, cutting and/or shapingthe ceramic article, and so forth.

The ceramic article is machined into a configuration that is appropriatefor a particular application. Prior to machining, the ceramic articlemay have a rough shape and size appropriate for a particular purpose(e.g., to be used as a lid in a plasma etcher). However, the machiningmay be performed to precisely control size, shape, dimensions, holesizes, and so forth of the ceramic article.

In one embodiment, the ceramic article is machined into a ceramic lid ora ceramic nozzle for a plasma etcher. The ceramic lid and ceramic nozzlein one embodiment are yttria dominant ceramics. Yttria dominant ceramicsmay be used due to the superior plasma resistance properties. In oneembodiment, the ceramic nozzle is pure yttria (Y₃O₂), and the ceramiclid is the HPM ceramic composite. The HPM ceramic composite may haveimproved flexural strength over pure Y₂O₃. Since the ceramic lid has alarge surface area, the HPM ceramic composite may be used for theceramic lid to prevent cracking or buckling during processing (e.g.,when a vacuum is applied to a process chamber of the plasma etcher). Inan alternative embodiment, the ceramic lid and the ceramic nozzle arecomposed of the same ceramic substance. For example, both the ceramiclid and the ceramic nozzle may be formed of the HPM ceramic composite.

The sintering process may result in the ceramic article having a certainroughness, surface defect density and/or quantity of trapped particles.The surface roughness and/or surface defect density may be made worse bythe machining process. Moreover, the machining process can generate alarge number of surface particles that adhere to the ceramic article.

For ceramic articles that are components of a semiconductor processingdevice (e.g., an etcher) that will be used for a plasma process, theincreased surface roughness, surface defect density and/or surfaceparticles may cause particle contamination to processed substrates. Forexample, surface defects in the ceramic article may include broken (oropen) bonds that are high energy locations. These surface defects maytrap particles. For example, the particles may form weak broken bondswith the ceramic article at the surface defect. During a plasmatreatment, the plasma may break these weak broken bonds, and remove someof the particles from the ceramic article. The ceramic particles maythen be deposited on a processed substrate. Moreover, the plasma maybreak bonds of the ceramic article at the defect sites, which may erodethe ceramic article and cause additional particles to be created.

At block 160, the ceramic article is heated at a ramping rate of about0.1° C. to about 20° C. per minute. Ceramic articles may be fragile, andmay crack when exposed to extreme changes in temperature. Accordingly, aramping rate that is slow enough to prevent the ceramic article fromcracking is used. It is expected that for some ceramics a ramping rateof more than 20° C. per minute may be possible. Accordingly, in someembodiments, ramping rates beyond 20° C. per minute that do not causecracking may be used.

The temperature changes that cause a ceramic article to crack may dependon the composition of the ceramic article. For example, Al₂O₃ may beheated at a rate of 10° C. per minute or more without cracking. However,Y₂O₃ may crack if heated at a ramping rate that is faster than about 5°C. per minute. In one embodiment, a ramping rate of about 0.1-5° C. perminute is used for Y₂O₃ and for the HPM ceramic composite. In a furtherembodiment, a ramping rate of about 1° C. per minute is used for Y₂O₃and for the HPM ceramic composite. Typically, the ceramic article willstart at or near ambient temperature, and will slowly be heated at theramping rate to a predetermined temperature.

The ceramic article is heated until it reaches a specified temperatureor temperature range. The specified temperature may range from about1000° C. to about 1800° C. The specific temperature used may depend onthe composition of the ceramic article. In one embodiment, a temperatureof 1600-1700° C. is used for the HPM ceramic composite and for yttria(Y₂O₃).

At block 165, the ceramic article is heat treated at the specifiedtemperature or at one or more temperatures within the temperature rangefor a duration of up to 24 hours. The specific duration used may dependon a composition of the ceramic article, as well as desired performanceproperties of the ceramic article. For example, an increased heattreatment duration may cause the ceramic article to produce fewerparticle contaminants than a shorter heat treatment duration. In oneembodiment, the heat treatment duration is about 3-6 hours for yttriaand for the HPM ceramic composite. In one embodiment, the heat treatmentduration is about 4 hours for yttria and for the HPM ceramic composite.

In one embodiment, the ceramic article is maintained at a singletemperature for the duration of the heat treatment. Alternatively, theceramic article may be heated and/or cooled to multiple differenttemperatures within the temperature range during the heat treatment. Forexample, the ceramic article may be heat treated at a temperature of1500° C. for 4 hours, may then be heat treated to a temperature of 1700°C. for another 2 hours, and may then be heat treated at 1000° C. foranother three hours. Note that when multiple different heat treatmenttemperatures are used, the ceramic article may be heated and/or cooledat the ramping rate to transition between heat treatment temperatures.

As discussed above, the ceramic article may have a high number ofsurface defects and particles that are trapped by these surface defects.The heat treatment may reduce or eliminate these defects and/orparticles. Specifically, the heat treatment may cause the particles tomelt and/or may cause a portion of the ceramic article to melt at thesurface defect regions. The melted particles may flow together with theceramic article at the surface defect regions. The melted particles maythen redeposit onto the ceramic article and form unbroken bonds with theceramic article at these surface defect regions. The resultant unbrokenbonds are much stronger than the broken bonds that previously bound theparticles to the ceramic article. Thus, the particles become much lesssusceptible to being removed from the ceramic article during a plasmaetch process, and the defect regions become less susceptible to erosion.

At block 170, the ceramic article is cooled at the ramping rate. In oneembodiment, the ceramic article is cooled at the same ramping rate asthe ramping rate used to heat the ceramic article. In anotherembodiment, a different ramping rate is used to cool the ceramic articlethan was used to heat the ceramic article. The resultant heat treatedceramic article may have improved performance with regards to bothparticle contamination of processed substrates and with regards toplasma erosion resistance. Thus, ceramic lids, ceramic nozzles and otherceramic internal process chamber components may be heat treated usingprocess 150 to improve yield of manufactured products. Moreover, ceramicarticles to which process 150 is applied may have a reduced replacementfrequency, and may reduce apparatus down time.

Note that process 150 may be performed as part of a manufacturingprocess after ceramic articles have been machined. Additionally, process150 may be periodically performed on used ceramic articles to heal orrepair those ceramic articles. For example, a ceramic article may beheat treated using process 150 before use, and may then be heat treatedusing process 150 every few months, once a year, twice a year, or atsome other frequency. The frequency with which to perform process 150may depend on plasma etch and/or plasma clean recipes that are used withthe ceramic article. For example, if the ceramic article is frequentlyexposed to particularly harsh plasma environments, then the ceramicarticle may be heat treated at an increased frequency.

Exposure to plasma may cause the ceramic article to erode and/or corrodeover time. For example, the plasma may cause broken bonds to occur atthe surface of the ceramic article, may generate ceramic particles thatcan contaminate processed substrates, may cause defects at the surfaceof the ceramic article, and so on. Accordingly, as a ceramic articleages, the more particle contamination it is likely to cause. The heattreatment process 150 may be performed on such aged ceramic articles toreverse damage caused by the corrosive plasma environment. The heattreatment may heal defects and reduce particles for used ceramicarticles in addition to newly manufactured ceramic articles.Accordingly, process 150 may be performed on used ceramic articles toprolong their useful life.

Note that in addition to healing surface defects and minimizingparticles, the heat treatment process 150 may also be used to dry cleanceramic articles. Exposure to plasma environments may cause polymers toform on a surface of the ceramic article. These polymers may causeparticle contamination on substrates during subsequent processing.Often, a periodic wet clean procedure is performed to remove thepolymers from the ceramic article. In one embodiment, heat treatmentprocess 150 is performed instead of or in addition to a wet cleanprocess. The heat treatment process 150 may cause the polymers that coatthe ceramic article to react with air or another gas in a hightemperature environment. This reaction may cause the polymer to becomegaseous, and to leave the surface of the ceramic article. Therefore, theheat treatment process 150 can be used both to clean the ceramic articleand to repair a surface of the ceramic article.

FIG. 2A shows micrographs 202-210 of a ceramic article at a 10,000-foldmagnification before the ceramic article is processed using a heattreatment, and after the ceramic article has been processed using heattreatments of various temperatures, in accordance with embodiments ofthe present invention. The ceramic article shown in micrographs 202-210is a HPM ceramic composite having Y₄Al₂O₉ and Y₂-xZr_(x)O₃ (a solutionof Y₂O₃—ZrO₂). Micrograph 202 shows a sample of the ceramic articleprior to heat treatment. Micrograph 204 shows the sample of micrograph202 after a 1200° C. heat treatment. Micrograph 206 shows the sample ofmicrograph 202 after a 1500° C. heat treatment. Micrograph 208 shows thesample of micrograph 202 after a 1600° C. heat treatment. Micrograph 210shows the sample of micrograph 202 after a 1700° C. heat treatment. Asshown, the surface morphology of the HPM ceramic composite significantlychanged above a 1500° C. heat treatment, causing surface roughness tosignificantly improve.

FIG. 2B shows micrographs 234-240 of an HPM composite ceramic article ata 4,000-fold magnification before the ceramic article is processed usinga heat treatment, and after the ceramic article has been processed usingheat treatments of various temperatures, in accordance with embodimentsof the present invention. Micrograph 232 shows a sample of the ceramicarticle prior to heat treatment. Micrograph 234 shows the sample ofmicrograph 232 after heat treatment at 1200° C. Micrograph 236 shows thesample of micrograph 232 after heat treatment at 1500° C. Micrograph 238shows the sample of micrograph 232 after heat treatment at 1600° C.Micrograph 240 shows the sample of micrograph 232 after heat treatmentat 1700° C. As shown, the heat treatment caused surface roughness tosignificantly improve and surface morphology to change.

FIG. 3A is a graph showing surface profiles of the ceramic articlesbefore heat treatment 310 and after the heat treatment 320, inaccordance with one embodiment of the present invention. The verticalaxis represents the surface profile variation from a baseline(represented as 0) in micro-inches, and the horizontal axis representsdistance across the surface of the ceramic article in thousandths of aninch. As shown, the number of defects that are deeper than about 70micro-inches are significantly reduced from about 8 defects deeper thanabout 70 micro-inches over 160 thousandths micro-inch to about 3 defectsdeeper than about 70 micro-inches over 160 thousandths micro-inch.Accordingly, the defect density for deep defects (e.g., defects greaterthan about 70 micro-inches or greater than 1 standard deviation fromaverage) may be reduced by 50% or more. Additionally, the uniformity andsurface roughness of the surface is improved in the post-heat treatedceramic article. A surface roughness as low as about 0.1μ-inch may beachieved in some embodiments. Post heat treatment, the ceramic articlemay have a surface roughness of about 0.1μ-inch to about 150μ-inch,depending on the type of ceramic, pre-heat treatment surface roughness,and so on. In one embodiment, post-heat treatment surface roughness isapproximately 20-60μ-inch.

FIG. 3B is a graph 320 showing a phase composition comparison of an HPMceramic composite before heat treatment 322, after a 1200° C. heattreatment 324 and after a 1680° C. heat treatment 326. As shown, theheat treatment may not change a phase composition of the HPM ceramiccomposite.

FIG. 4A shows micrographs 402-406 of a solid yttria ceramic article at a10,000-fold magnification before and after the solid yttria ceramicarticle is processed using a heat treatment, in accordance with oneembodiment of the present invention. Micrograph 402 shows a sample ofthe ceramic article prior to heat treatment. Micrograph 404 shows thesample of micrograph 402 after heat treatment at 1500° C. Micrograph 406shows the sample of micrograph 402 after heat treatment at 1700° C. Asshown, the heat treatment caused surface morphology to change,significantly improving roughness and removing particles and potentialparticles.

FIG. 4B shows micrographs 422-426 of a solid yttria ceramic article at a4,000-fold magnification before and after the solid yttria ceramicarticle is processed using the heat treatment, in accordance with oneembodiment of the present invention. Micrograph 422 shows a sample ofthe ceramic article prior to heat treatment. Micrograph 424 shows thesample of micrograph 422 after heat treatment at 1500° C. Micrograph 426shows the sample of micrograph 422 after heat treatment at 1700° C. Asshown, the heat treatment caused surface roughness to significantlyimprove.

FIG. 5 is a graph showing surface profiles of the solid yttria ceramicarticle of FIGS. 4A-4B before the heat treatment 510 and after the heattreatment 520, in accordance with one embodiment of the presentinvention. The vertical axis represents the profile variation inmicro-inches, and the horizontal axis represents distance across thesurface in thousandths of an inch. As shown, the number of defects thatare deeper than about 100 micro-inches are significantly reduced, as isthe depth of these defects. For example, prior to the heat treatment,there were at least two defects over 160 thousandths of an inch thatwere nearly 200 micro-inches deep. In contrast, there were no surfacedefects with those depths after the heat treatment. Additionally, theuniformity of the surface is improved in the post-heat treated ceramicarticle.

TABLE 1 Surface Morphology Pre-Heat Treatment and Post-Heat TreatmentR_(z) RHSC P_(mr) R_(a) (μ-inch) (μ-inch) (unitless) (%) HPM Pre-HeatTreatment 23.86 176.29 19 1.94 Post-Heat Treatment 20.46 156.83 29 2.16Y2O3 Pre-Heat Treatment 32.21 222.26 18 0.95 Post-Heat Treatment 26.26198.65 29 1.88

Table 1 shows a surface morphology of HPM and yttria ceramic articlesbefore and after performing a heat treatment on the ceramic articles, inaccordance with embodiments of the present invention. The surfacemorphology shown in Table 1 is based on measurements of the HPM andyttria ceramic articles illustrated in FIGS. 2A-5.

The surface morphology may be represented using surface roughnessparameters and/or surface uniformity parameters. Measured parametersthat represent surface roughness are average roughness (R_(a)) andmaximum peak to valley height (R_(z)). R_(a) may be determined bycomputing an arithmetic average of the absolute values of roughnessprofile ordinates within a specified window. R_(a) may be computed byfinding and measuring the greatest peak to valley distance within thewindow. R_(a) and r_(z) have units of measurement in micro-inches(μ-inches) in Table 1. Lower values of R_(a) and R_(z) represent asmoother surface, and may be indicators of improved performance withregards to particle contamination.

Measured parameters that represent surface uniformity are high spotcount (RHSC) and bearing length ratio (P_(mr)). RHSC is computed bydetermining a cut height based on subtracting a depth value from ahighest peak within the window, and then counting a number of peaks thatexceed the cut height. P_(mr) is computed by adding up peak widths ofthe peaks at the cut height, and computing a percentage of the windowthat is filled by the sum of the peak widths. The depth value used todetermine the cut height for RHSC and P_(mr) in Table 1 is 20μ-inches.Higher values of RHSC and P_(mr) represent greater uniformity, and maybe indicators of improved performance with regards to particlecontamination.

As shown, the R_(a), R_(z), RHSC and P_(mr) values for both the HPM andyttria ceramic articles improved as a result of the heat treatment. Inone embodiment, centerline average surface roughness (R_(a)) is improvedby about 3-5μ-inches or about 10-20% for HPM ceramic articles and byabout 5-10 μ-inches or about 15-30% for yttria ceramic articles. Asshown, post treatment surface roughness for HPM ceramic articles may bearound 20μ-inches and post heat treatment surface roughness for yttriaceramic articles may be around 26μ-inches in one embodiment. Empiricalevidence also shows that the amount of particle contamination causedduring plasma etch processes by ceramic lids and ceramic nozzles isdecreased as a result of the heat treatment.

FIG. 6 is a chart 600 showing surface particle count of an HPM compositeceramic before and after heat treatment, in accordance with oneembodiment of the present invention. In chart 600, measured particleshave a size greater than or equal to 0.2 microns. As shown, the particlecount prior to heat treatment is in excess of 200,000 particles persquare centimeter, with a range of about 210,000 particles to about250,000 across samples (e.g., 230,000±20,000 particles per squarecentimeter). However, the particle count after a heat treatment at 1600°C. is about 15,000±1,000 particles per square centimeter. Accordingly,the surface particle count may be significantly improved by performingheat treatments described herein. In one embodiment, the surfaceparticle count may improve by over 200,000 particles per squarecentimeter, which is in improvement of as much as about 93%.

FIG. 7 is another chart 700 showing surface particle count (in thousandsof particles) of an HPM composite ceramic before heat treatment andduring heat treatment at various temperatures, in accordance withembodiments of the present invention. In chart 700, measured particlesmay have a size greater than or equal to 0.2 microns. As shown, theparticle count prior to heat treatment is about 180,000 particles persquare centimeter. The particle count increases in relation totemperature increases for heat treatments up to around 500° C. Theparticle count then decreases in relation to temperature increases forheat treatments of about 500° C. to about 1200° C.

Note that for heat treatments of up to about 1200° C., the interactionbetween particles and a surface of the ceramic article may be dominatedby a van der Waals force, according to the following equation:

$\begin{matrix}{F = \frac{A}{12\;\pi\; H^{2}}} & \left( {{equation}\mspace{14mu} 1} \right)\end{matrix}$where F is force, A is area and H is distance. As the heat treatmenttemperature increases from room temperature to about 500° C., the vander Wall force may weaken, and thermal expansion may induce an increasein the distance H. As the heat treatment temperature increases from 500°C. to about 1200° C., the van der Waal force may strengthen due at leastin part to decreases in the distance H. Such reductions in distance maybe due to the substrate surface absorbing particles and/or deformations.

At temperatures between about 1200° C. and 1800° C., a liquid film maybe formed between particles and the substrate surface. Between about1200° C. and 1500° C., the liquid film may be a thin liquid film, andbetween about 1500° C. and 1800° C., the liquid film may be a thickliquid film. At temperatures up to about 1800° C., the interactionbetween the particles and the substrate surface may be dominated byinteraction through the liquid by a capillary force, according to thefollowing equation:F=4πγR cos θ  (equation 2)where F is force, γ is liquid-air surface tension, R is effective radiusof the interface between the particles and substrate surface, and 0 iscontact angle. At these temperatures, particles may be diffused into theliquid, and may be re-grown on a corresponding grain. This may causeparticles to be removed from the substrate surface, even after theceramic article has cooled.

For the HPM ceramic composite and yttria, 1800° C. is the sinteringtemperature. Accordingly, at temperatures at or above around 1800° C., aliquid phase is formed in the bulk of the substrate between powders.These powders may melt into liquid and grow into grains of increasingsize. Atoms may be diffused from high energy grains to low energy grainsuntil an equilibrium is reached. Accordingly, in one embodiment, theheat treatment is performed at temperatures below about 1800° C.

The preceding description sets forth numerous specific details such asexamples of specific systems, components, methods, and so forth, inorder to provide a good understanding of several embodiments of thepresent invention. It will be apparent to one skilled in the art,however, that at least some embodiments of the present invention may bepracticed without these specific details. In other instances, well-knowncomponents or methods are not described in detail or are presented insimple block diagram format in order to avoid unnecessarily obscuringthe present invention. Thus, the specific details set forth are merelyexemplary. Particular implementations may vary from these exemplarydetails and still be contemplated to be within the scope of the presentinvention.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure, orcharacteristic described in connection with the embodiment is includedin at least one embodiment. Thus, the appearances of the phrase “in oneembodiment” or “in an embodiment” in various places throughout thisspecification are not necessarily all referring to the same embodiment.In addition, the term “or” is intended to mean an inclusive “or” ratherthan an exclusive “or.”

Although the operations of the methods herein are shown and described ina particular order, the order of the operations of each method may bealtered so that certain operations may be performed in an inverse orderor so that certain operation may be performed, at least in part,concurrently with other operations. In another embodiment, instructionsor sub-operations of distinct operations may be in an intermittentand/or alternating manner.

It is to be understood that the above description is intended to beillustrative, and not restrictive. Many other embodiments will beapparent to those of skill in the art upon reading and understanding theabove description. The scope of the invention should, therefore, bedetermined with reference to the appended claims, along with the fullscope of equivalents to which such claims are entitled.

What is claimed is:
 1. A heat-treated ceramic article prepared by aprocess comprising: heating a machined ceramic article to a temperaturerange between about 1000° C. and about 1800° C., wherein the machinedceramic article comprises an uncoated bulk sintered ceramic comprising arare earth oxide, the machined ceramic article has a surface with aninitial surface defect density and an initial surface roughness, theinitial surface defect density is based on a plurality of surfacedefects, the plurality of surface defects comprises a plurality ofbroken bonds having surface particles bound thereto, and the surfaceparticles comprise the rare earth oxide and are formed by breaking ofbonds of the machined ceramic article to form the plurality of brokenbonds; heat treating the machined ceramic article at one or moretemperatures within the temperature range for a duration of up to about24 hours, the heat treating comprising: melting a layer of the machinedceramic article at the surface, wherein at least a fraction of thesurface particles are melted to produce melted surface particles;diffusing the melted surface particles comprising the rare earth oxideinto the plurality of surface defects at the melted layer to formunbroken bonds with the layer at the plurality of surface defects; andre-growing the melted surface particles comprising the rare earth oxideon grains of the machined ceramic article; and cooling the machinedceramic article, wherein the heating and cooling are each performed at aramping rate of less than about 5° C. per minute to avoid cracking ofthe machined ceramic article, and wherein the heat-treated ceramicarticle has a reduced surface defect density that is lower than theinitial surface defect density, a reduced amount of surface particlescomprising the rare earth oxide that are trapped by broken bonds, and areduced surface roughness, caused by the heat treating that comprises anaverage roughness of about 26.26 μ-inch or less and a maximum peak tovalley height of about 198.65 μ-inch or less, wherein the reducedsurface roughness is lower than the initial surface roughness.
 2. Theheat-treated ceramic article of claim 1, wherein the machined ceramicarticle is a bulk ceramic article consisting essentially of at least oneof Al₂O₃, AlON, Y₄Al₂O₉ (YAM), YAlO₃, Al₂O₃-YAG, Quartz, SiC, Sialon,Si₃N₄, AN, TiO₂, ZrO₂, TiC, TiCN, ZrC, SiC, TiN, SiC—Si₃N₄, or Y₂O₃stabilized ZrO₂.
 3. The heat-treated ceramic article of claim 1, whereinthe machined ceramic article comprises a compound of Y₄Al₂O₉ and asolid-solution of Y₂O₃—ZrO₂, wherein the compound is formed from about55-77 mol % Y₂O₃, about 15-23 mol % ZrO₂, and about 8-25 mol % Al₂O₃. 4.The heat-treated ceramic article of claim 1, wherein the heat treatingis performed in at least one of a vacuum or presence of N₂.
 5. Theheat-treated ceramic article of claim 1, wherein the heat-treated heattreated ceramic article is one of a lid for a plasma etcher or a nozzlefor the plasma etcher.
 6. The heat-treated ceramic article of claim 1,wherein the reduced surface roughness of the heat-treated ceramicarticle is approximately 10-30% less than the initial surface roughness,and wherein the reduced amount of surface particles is about 50-90% lessthan an initial surface particle count of the machined ceramic article.7. The heat-treated ceramic article of claim 1, wherein the machinedceramic article comprises Y₂O₃.
 8. The heat-treated ceramic article ofclaim 1, wherein the machined ceramic article comprises Y₃Al₅O₁₂ (YAG).9. The heat-treated ceramic article of claim 1, the process furthercomprising: after the heat-treated ceramic article has been used in aplasma etch process, repeating the heating, the heat treating and thecooling to reduce an increased surface defect density caused by theplasma etch process.
 10. The heat-treated ceramic article of claim 9,wherein the plasma etch process causes polymers to form on theheat-treated ceramic article, and wherein repeating the heat treating inpresence of oxygen dry cleans the heat-treated ceramic article bycausing the polymers to react with the oxygen to become gases.
 11. Theheat-treated ceramic article of claim 1, wherein the heat-treatedceramic article has a defect density of surface defects having a depthof deeper than about 70 μ-inch that is at least 50% less than an initialdefect density of surface defects having the depth of deeper than about70 μ-inch of the machined ceramic article.
 12. The heat-treated ceramicarticle of claim 1, wherein the reduced amount of surface particles isabout 90% less than an initial amount of surface particles of themachined ceramic article, wherein each particle of the reduced amount ofsurface particles and the initial amount of surface particles has a sizethat is equal to or greater than 0.2 microns.
 13. The heat-treatedceramic article of claim 1, wherein the temperature range is over 1600°C. to under 1800° C.
 14. The heat treated ceramic article of claim 13,wherein the temperature range is from about 1700° C. to under 1800° C.15. The heat-treated ceramic article of claim 1, wherein the heattreating further comprises: melting the surface particles trapped by theplurality of surface defects; flowing together the melted surfaceparticles with the melted layer of the ceramic article at regions of theplurality of surface defects; and redepositing the melted surfaceparticles onto the machined ceramic article at the regions of theplurality of surface defects to form a plurality of unbroken bonds. 16.The heat-treated ceramic article of claim 1, wherein: the reduced amountof surface particles is, caused by the heat treating, lower than aninitial amount of surface particles of the machined ceramic article; thereduced amount of surface particles is about 14,000 to 16,000 particlesper square centimeter; the heat-treated ceramic article has, caused bythe heat treating, an increased surface uniformity that is greater thanan initial surface uniformity of the machined ceramic article; and theincreased surface uniformity comprises about 29 high spot count (HSC) orgreater and about 1.88% bearing rate ratio (P_(mr)) or greater.
 17. Aheat-treated ceramic article prepared by a process comprising: heating amachined ceramic article to a temperature range between about 1000° C.and about 1800° C.; heat treating the machined ceramic article at one ormore temperatures within the temperature range for a duration of up toabout 24 hours; and cooling the machined ceramic article, wherein theheat-treated ceramic article has a reduced amount of surface particlesthat is about 14,000 to 16,000 particles per square centimeter, whereinthe reduced amount of surface particles is lower than an initial amountof surface particles of the machined ceramic article.
 18. Theheat-treated ceramic article of claim 17, wherein the heating and thecooling are each performed at a ramping rate of less than about 5° C.per minute to avoid cracking of the machined ceramic article.
 19. Aheat-treated ceramic article prepared by a process comprising: heating amachined ceramic article to a temperature range between about 1000° C.and about 1800° C.; heat treating the machined ceramic article at one ormore temperatures within the temperature range for a duration of up toabout 24 hours; and cooling the machined ceramic article, wherein theheat-treated ceramic article has an increased surface uniformity thatcomprises about 29 high spot count (HSC) or greater, wherein theincreased surface uniformity is greater than an initial surfaceuniformity of the machined ceramic article.
 20. The heat-treated ceramicarticle of claim 19, wherein: the heating and the cooling are eachperformed at a ramping rate of less than about 5° C. per minute to avoidcracking of the machined ceramic article; and the increased surfaceuniformity further comprises about 1.88% bearing rate ratio (P_(mr)) orgreater.